Washing and cleaning process

ABSTRACT

A washing and cleaning process which comprises adding to the corresponding liquor comprising a peroxide-containing washing and cleaning agent 1 to 500 millimoles per liter of liquor of one or more than one compound of the salene type.

The present invention relates to novel catalysts which significantlyimprove the bleaching effect of hydrogen peroxide in the treatment oftextile material without causing any substantial damage to fibre anddyeings, and to washing and cleaning agent formulations comprising thesecatalysts as well as to a method for cleaning and/or bleachingsubstrates which uses such washing and cleaning agent formulations.

Peroxide-containing bleaches have been used for some time in washing andcleaning processes. At a liquor temperature of 90° C. or more they arehighly effective. As the temperature drops, however, their performancedecreases markedly. It is known that diverse transition metal ions,added in the form of suitable salts or co-ordination compoundscontaining such cations, catalyse the degradation of H₂O₂. In this wayit is possible to increase the bleaching effect of H₂O₂, or ofprecursors releasing H₂O₂ and also of other peroxide compounds, whicheffect is insufficient at lower temperatures. Important in practice arein this case only those combinations of transition metal ions andligands, the peroxide activation of which is also expressed in anenhanced readiness to oxidise with regard to the substrate and not onlyin a catalase-like disproportionation, for the latter activation, whichis unwanted in the present case, can further diminish the bleachingeffects of H₂O₂ and its derivatives, which are insufficient at lowtemperatures.

As regards bleaching-effective H₂O₂ activation, mono- and polynuclearvariants of manganese complexes with diverse ligands, in particular with1,4,7-trimethyl-1,4,7-triazazyclononane and, optionally,oxygen-containing bridging ligands, are held to be particularlyeffective at present. Such catalysts are sufficiently stable underpractice conditions and contain the ecologically safe metal cationMn^((n+)). However, their use entails substantial damage to dyes andfibres. The catalysts of this invention, however, are capable ofsignificantly increasing the bleaching effect of H₂O₂ without causingany substantial damage to the washing goods.

Accordingly, this invention relates to a washing and cleaning process,which comprises adding to the liquor comprising a peroxide-containingwashing and cleaning agent 1-500 μmol per litre of liquor of a compoundof formula

wherein

n is 0, 1, 2 or 3,

m is 1, 2 or 3,

R₄ is hydrogen or linear or branched C₁—C₄alkyl,

R₈ is hydrogen or linear or branched C₁—C₄alkyl,

Y is a linear or branched alkylene radical of formula —[C(R₄)₂]_(r)—,wherein r is an integer from 1 to 8, and the R₄ groups have eachindependently of one another the meaning given above;

—CX═CX—, wherein X is cyano, linear or branched C₁-C₈alkyl or di(linearor branched C₁-C₈alkyl)amino,

—(CH₂)_(q)—NR₄—(CH₂)_(q)—, wherein R₄ has the meaning cited above, and qis 1, 2, 3 or 4; or a 1,2-cyclohexylene radical of formula:

or a 1,2-aryl radical of formula

wherein R₉ is hydrogen, SO₃H, CH₂OH or CH₂NH_(2,)

R and R₁ are each independently of the other cyano, halogen, OR₄ orCOOR₄, wherein R₄ has the meaning cited above, nitro, linear or branchedC₁-C₈alkyl, linear or branched partially fluorinated or perfluorinatedC₁-C₈alkyl, NR₅R₆, wherein R₅ and R₆ are identical or different and areeach hydrogen or linear or branched C₁-C₁₂alkyl, or linear or branchedC₁-C₈alkyl-R₇, wherein R₇ is NH₂, OR₄, COOR₄ or NR₅R₆, which have themeanings given above, or —CH₂—N⊕R₄R₆R₇ or —N⊕R₄R₅R₆, wherein R₄, R₅ andR₆ have the meanings cited above, R₂ and R₃ are each independently ofthe other hydrogen, linear or branched C₁-C₄alkyl or unsubstituted aryl,or aryl which is substituted by cyano, halogen, OR₄ or COOR₄, wherein R₄is hydrogen or linear or branched C₁-C₄alkyl, by nitro, linear orbranched C₁-C₈alkyl, NHR₅ or NR₅R₆, wherein R₅ and R₆ are identical ordifferent and are each hydrogen or linear or branched C₁-C₁₂alkyl, or bylinear or branched C₁-C₈alkyl-R₇, wherein R₇ is NH₂, OR₄, COOR₄ orNR₅R₆, which have the meanings given above, or by —N⊕R₄R₅R₆, wherein R₄,R₅ and R₆ have the meanings given above.

It is preferred to add 5 to 350 μmol, preferably 10 to 250 μmol, perlitre of washing liquor, of a compound of formula (1) or (2) to thewashing and cleaning liquor.

If, in the compounds of formula (1), R and/or R₁ is —N⊕R₄R₅R₆, or R₂and/or R₃ are —N⊕R₄R₅R₆-substituted aryl, wherein R₄, R₅ and R₆ have themeanings cited above, then suitable anions for balancing the positivecharge at the —N⊕R₄R₅R₆ group are halides, such as chloride, bromide andiodide, perchlorate, sulfate, nitrate, hydroxide, BF₄ ⁻, PF₆ ⁻,carboxy-late, acetate, tosylate or triflat. Bromide, chloride and iodideare preferred.

In those compounds of formula (1) wherein n is 2 or 3, the R groups mayhave the same or different meanings. The same applies to compounds offormula (1), where m is 2 or 3, with respect to the R₁ groups.

Y defined as a 1,2-cyclohexylene radical may be in any of itsstereoisomeric cis/trans forms.

Y is preferably a radical of formula —(CH₂)_(r)—, wherein r is aninteger from 1 to 8, or of formula —C(R₄)₂—(CH₂)_(p)—C(R₄)₂—, wherein pis a number from 0 to 6, preferably from 0 to 3, and the R₄ groups areeach independently of one another hydrogen or C₁-C₄alkyl, preferablyhydrogen or methyl, or a 1,2-cyclohexylene radical or a 1,2-phenyleneradical of formula:

Halogen is preferably chloro, bromo or fluoro. Chloro is particularlypreferred.

If n or m is 1, the R and R₁ groups are preferably in 4-position of therespective benzene ring unless R or R₁ is nitro or COOR₄. In that casethe R or R₁ group is preferably in 5-position. If R or R₁ is N⊕R₄R₅R₆,the R or R₁ group is preferably in 4- or 5-position.

If n or m is 2, the two R or R₁ groups are preferably in 4,6-position ofthe respective benzene ring unless R or R₁ is nitro or COOR₅. In thatcase, the R or R₁ groups are preferably in 3,5-position.

If R or R₁ is di(C₁-C₁₂alkyl)amino, then the alkyl group may bestraight-chain or branched. The alkyl group preferably contains 1 to 8,more preferably 1 to 3, carbon atoms.

R and R₁ are preferably hydrogen, OR₄, COOR₄, N(R₄)₂ or N⊕(R₄)₃, whereinin N(R₄)₂ or N⊕(R₄)₃ the R₄ groups may be different and are hydrogen orC₁-C₄alkyl, preferably methyl, ethyl or isopropyl.

R₂ and R₃ are preferably hydrogen, methyl, ethyl or unsubstitutedphenyl.

In particularly preferred compounds of formula (2) R₈ is hydrogen.

Aryl is typically naphthyl or, preferably, phenyl.

Particularly interesting compounds for use in the novel process arethose of formulae

The compounds of formula (1) and (2) are known or can be prepared in amanner known per se. General methods of preparation are described, interalia, in U.S. Pat. No. 5,281,578 and by Bernardo et al. in Inorg. Chem.35 (1996) 387.

The compounds of formula (1) or (2) can be used singly or in admixturewith two or more compounds of formula (1) or (2).

It is also possible to use the compounds of formula (1) or (2) togetherwith transition metal salts or complexes, for example with compounds orsalts of manganese, iron, cobalt or copper. Suitable are, for example,the salene complexes which are disclosed in the European patentapplications No. 98810870.0 and 98810289.3.

This invention also relates to a washing and cleaning agent, whichcomprises

I) 5-90%, preferably 5-70%, A) of an anionic surfactant and/or B) of anonionic surfactant,

II) 5-70%, preferably 5-50%, more preferably 5-40%, C) of a buildersubstance,

III) 0.1-30%, preferably 1-12%, D) of a peroxide, and

IV) a compound of formula (1) or (2) in an amount which in the washingor cleaning process results in a 1-500 μmolar, preferably 5-350 μmolar,more preferably 10-250 μmolar, solution.

The washing and cleaning agent can be in solid or liquid form, forexample in the form of a liquid non-aqueous agent, containing not morethan 5% by weight, preferably 0 to 1% by weight, of water, and as basisa suspension of a builder substance in a nonionic surfactant, as isdescribed, inter alia, in GB-A-2,158,454.

However, the washing and cleaning agent is preferably in powdered orgranulated form which may be produced, for example, by first preparing astarting powder by spray-drying an aqueous slurry, containing all of theabove components except the components D) and E), and then adding thedry components D) and E) and mixing all of the components. It is alsopossible to add the component E) to an aqueous slurry containing thecomponents A), B) and C) and, after spray-drying this mixture, mixingthe component D) with the dry mixture.

It is also possible to start from an aqueous slurry which contains thecomponents A) and C), but not, or only partially, component B). Afterspray-drying the slurry, the component E) is mixed with the component B)and added thereto, and the component D) is then admixed in dry form.

The anionic surfactant A) may be, for example, a sulfate, sulfonate orcarboxylate surfactant, or a mixture thereof. Preferred sulfates arethose which contain 12-22 carbon atoms in the alkyl radical, optionallyin combination with alkylethoxysulfates, the alkyl radical of whichcontains 10-20 carbon atoms.

Preferred sulfonates are, for example, alkylbenzenesulfonates containing9-15 carbon atoms in the alkyl radical. The cation in the anionicsurfactants is preferably an alkali metal cation, more preferablysodium.

Preferred carboxylates are alkali metal sarcosinates of formulaR—CO—N(R¹)—CH₂COOM¹, wherein R is alkyl or alkenyl containing 8 -18carbon atoms in the alkyl or alkenyl radical, R¹ is C₁-C₄alkyl, and M¹is an alkali metal.

The nonionic surfactant B) may be, for example, a condensate of 3-8 molof ethylene oxide with 1 mol of primary alcohol containing 9-15 carbonatoms.

Suitable builder substances C) are, for example, alkali metalphosphates, preferably tripolyphosphates, carbonates or bicarbonates,more preferably their sodium salts, silicates, aluminium silicates,polycarboxylates, polycarboxylic acids, organic phosphonates,aminoalkylenepoly(alkylenephosphonates), or mixtures of these compounds.

Particularly suitable silicates are the sodium salts of crystallinesheet silicates of formula NaHSi_(t)O_(2t+1).pH₂O orNa₂Si_(t)O_(2t+1).pH₂O, wherein t is a number from 1.9 to 4, and p is anumber from 0 to 20.

Preferred aluminium silicates are those which are commercially availableunder the names Zeolite A, B, X and HS as well as mixtures containingtwo or more of these components.

Preferred polycarboxylates are the polyhydroxycarboxylates, inparticular citrates, and acrylates as well as their copolymers withmaleic anhydride. Preferred polycarboxylic acids are nitrilotriaceticacid, ethylenediaminetetracetic acid, ethylenediaminedisuccinate both inracemic form and in (S,S)-form.

Particularly suitable phosphonates oraminoalkylenepoly(alkylenephosphonates) are the alkali metal salts of1-hydroxyethane-1,1-diphosphonic acid, nitrilotris(methylenephosphonicacid), ethylenediaminetetramethylenephosphonic acid anddiethylenetriaminepentamethylenephosphonic acid.

Suitable peroxide components D) are, for example, the organic andinorganic peroxides known in the literature and available on the market,which bleach textile materials at the standard washing temperatures, forexample from 10 to 95° C. The organic peroxides are, for example, mono-or polyperoxides, preferably organic peracids or the salts thereof, suchas phthalimidoperoxycapronic acid, peroxybenzoic acid, diperoxy dodecanediacid, diperoxynonane diacid, diperoxydecane diacid, diperoxyphthalicacid or the salts thereof.

However, it is preferred to use inorganic peroxides, such aspersulfates, perborates, percarbonates or persilicates. It is of coursealso possible to use mixtures of inorganic and/or organic peroxides. Theperoxides can be in different crystal forms and may have different watercontents, and they may also be used together with other inorganic ororganic compounds in order to improve their storage stability.

The peroxides are preferably added to the washing and cleaning agent bymixing the components, for example by means of a screw feeding systemand/or a fluidised bed mixer.

In addition to the novel combination, the washing and cleaning agentsmay contain one or more than one fluorescent whitening agent, forexample from the class of the bis-triazinylaminostilbenedisulfonic acid,bis-triazolylstilbenedisulfonic acid, bis-styrylbiphenyl orbis-benzofuranylbiphenyl, a bis-benzoxalyl derivative,bis-benzimidazolyl derivative, a coumarine derivative or a pyrazolinederivative.

The washing and cleaning agents may also contain suspending agents fordirt, for example sodium carboxymethylcellulose, pH-regulators, e.g.alkali or alkaline earth metal silicates, foam regulators, e.g. soaps,salts for regulating the spray-drying and the granulation properties,e.g. sodium sulfate, fragrances and, optionally, antistatic agents andsofte ners, enzymes such as amylase, bleaching agents, bleachingactivators such as TAED (tetraacetylethylenediamine) or SNOBS (sodiumnonanoyloxybenzene sulfonate), pigments and/or shading agents. Thesecomponents must, of course, be stable against the bleaching agent used.

Other additives preferably added to the novel washing and cleaningagents are polymers which prevent staining during the washing of thetextiles through dyes that are present in the liquor and that haveseparated from the textiles under the washing conditions. Theseadditives are preferably polyvinylpyrrolidones which are unmodified ormodified through the incorporation of anionic or cationic substituents,in particular those having a molecular weight in the range from 5'000 to60'000, preferably from 10'000 to 50'000. These polymers are preferablyused in an amount from 0.05 to 5% by weight, preferably from 0.2 to 1.7%by weight, based on the entire weight of the washing agent.

The following non-limitative Examples illustrate the invention in moredetail. Parts and percentages are by weight, unless otherwise stated.

EXAMPLE 1

The bleaching tests are carried out as follows: 7.5 g of a white cottonfabric and 2.5 g of a cotton fabric stained with tea, red wine orblackberries are treated in 80 ml of a washing liquor. This liquorcomprises the standard washing agent ECE phosphate-free (456 IEC) EMPA,Switzerland, in a concentration of 7.5 g/l and the oxidants, catalystsand, optionally, activators in the concentrations listed in thecorresponding Tables. The washing process is carried out in a steelbeaker in a LINITEST apparatus over 30 minutes at 40° C. To evaluate thebleaching results, the increase in brightness DY (difference inbrightness according to CIE) resulting from the treatment of thestainings is used. Table 1 contains the DY values for all 3 stainings oncotton after treatment with the systems a) to n).

TABLE 1 Increase of brightness DY at 40° C. in the system* Cottonstaining with a) b) c) d) e) f) g) h) i) j) k) l) m) n) tea 0 18 27 2524 21 24 21 23 23 25 25 24 23 red wine 3 11 22 23 21 17 22 15 18 16 1922 20 20 blackberries 8 20 31 22 21 22 27 22 23 23 21 26 21 20 *a)Washing liquor without bleaching system. B) Washing liquor with 8.6mmol/l of H₂O₂. c) Washing liquor with 1.125 g/l of sodium perboratemonohydrate and 0.3 g/l of TAED. d) Washing liquor with 8.6 mmol/l ofH₂O₂ and 5 μmol/l of catalyst A. e) Washing liquor with 8.6 mmol/l ofH₂O₂ and 100 μmol/l of catalyst 1a. f) to n) Idem, but with thecatalysts 1b to 1j

Catalyst A:

EXAMPLE 2

The bleaching effect of the novel catalysts is also tested at 20° C. Thetests and the evaluation of the bleaching results are carried outsimilarly to the procedure of Example 1. Table 2 contains the DY valuesfor the tea stainings on cotton after treatment with the systems a) ton).

TABLE 2 Increase of brightness DY at 20° C. in the system* Cottonstaining with a) b) c) d) e) f) g) h) i) j) k) l) m) n) tea 0 5 16 21 143 15 16 21 16 10 18 13 16 *a) Washing liquor without bleaching system.B) Washing liquor with 8.6 mmol/l of H₂O₂. c) Washing liquor with 1.125g/l of sodium perborate monohydrate and 0.3 g/l of TAED. d) Washingliquor with 8.6 mmol/l of H₂O₂ and 5 μmol/l of catalyst A. e) Washingliquor with 8.6 mmol/l of H₂O₂ and 100 μmol/l of catalyst 1a. f) to n)Idem, but with the catalysts 1b to 1j

EXAMPLE 3

Use of the novel catalysts causes hardly any additional bleaching of thedyes in dyed cotton washing goods. When used as described above, onaverage almost the same relative dye losses are obtained after 5treatments—even in the case of dyes known to be very sensitive—as in thebleach-free system. The values in Table 3 are relative dye losses inpercent, determined on the basis of Kubelka-Munk values in therespective absorption maximum.

TABLE 3 Cotton staining Relative decrease (%) in the system* with dye a)b) c) d) e) f) g) h) i) j) k) l) m) n) Vat Blue 4 10 10  5 20 35  5  5 5  5 15 30 10 15 25 Reactive Brown 17 10 20 15 45 15  5 15 15 10 15 1510 15 15 Reactive Black  5 10 10 30 45 15 10 10 10 10 10 15 10 10 10 VatBrown 1  5  0  0  0  5  0  0  5  5  5  0  0  0  0 Reactive Red 123 10 1515 40  5  5  5 10  5 10 10  5  5  5 Direct Blue 85 20 20 15 15 20 20 1520 20 25 15 15 10 15 *a) to n) as in Table 1.

EXAMPLE 4

The novel catalysts are used in an extremely fibre-preserving manner.When used as described above, the same relative decreases in the averagedegree of polymerisation are found after five treatments—even in thecase of cotton dyeings known to be highly susceptible to fibre damage—asin the bleach-free system, see Table 4.

TABLE 4 Cotton dyeing with Relative decrease (%) in the system* dye a)b) c) d) e) Vat Blue 4 5 5 5 40 5 Reactive Brown 17 0 0 5 50 0 ReactiveBlack 5 0 0 0 20 0 Vat Brown 1 10  5 20  55 5 Reactive Red 123 5 0 5 405 Direct Blue 85 10  5 0  5 10  *a) to d) as in Table 1. e) Washingliquor with 8.6 mmol/l H₂O₂ and 200 μmol/l of catalyst 1b.

EXAMPLE 5

Preparation of

A suspension of 500 mg (1.92 mmol) of3-formyl-4-hydroxyphenyltrimethylammonium bromide [synthesis instructionM. Ando, S. Emoto, Bull. Chem. Soc. Jpn, Vol.51 (8) 2433 (1978)] in 2 mlethanol is charged dropwise at 50° C. with 105 mg (0.915 mmol) oftrans-1,2-diaminocyclohexane. The reaction mixture is kept at 80° C. for4 h. After cooling to room temperature, the resulting precipitate iscollected by filtration, washed with a small amount of cold ethanol anddried under a high vacuum at 40° C. until the mass is constant. Yield:435 mg (79%) of a yellowish solid.

¹³C NMR (DMSO-d₆) δ=19.8, 25.5 27.4, 29.2 (cycl. CH₂), 53.4 (NCH₃), 63.6(CH₂—CH) 118.7, 121.9, 123.1 (tert aryl-C), 111.4, 131.5, 172.4 (quart.aryl-C), 163.2 (C═N).

EXAMPLE 6

Preparation of

The synthesis and working up are carded out as in Example 5, startingfrom 500 mg (1.92 mmol) of 4-formyl-3-hydroxyphenyltrimethylammoniumbromide and 0.105 g (0.915 mmol) of trans-1,2-diaminocylohexane. Yield:299 mg (55%).

¹³C NMR (D₂O) δ=23.6, 29.5, 31.3, 33.1 (cycl. CH₂), 56.8 (NCH₃), 67.3(CH₂—CH), 107.5, 112.0, 136.1 (tert aryl-C), 117.3, 152.4, 170.9 (quart.aryl-C), 166.6 (C═N).

EXAMPLE 7

Preparation of

A solution of 500 mg (2.79 mmol) of4-(N-ethyl-N-methylamino)salicylaldehyde is charged dropwise at roomtemperature with a solution of 80 mg (1.33 mmol) of ethylenediamine, andthis reaction solution is warmed for 4 h to 70° C. After cooling to roomtemperature, the resulting precipitate is collected by filtration,washed with a small amount of cold ethanol and dried in a vacuum dryingoven at 30° C. Yield: 476 mg (94%).

¹H NMR (CDCl₃) δ=1.13 (m, 6H, CH ₃—CH₂), 2.92 (s, 6H, NCH₃), 3.38 (m,4H, CH₃—CH ₂), 3.76 (s, 4H, NCH₂), 6.12 (m, 4H, aryl-H), 6.98 (m, 2H,aryl-H), 8.08 (s, 2H, CH═N), 13.52 (s, br, 2H, OH).

¹³C NMR (CDCl₃) δ=11.7 (CH₃—CH₂), 37.4 (NCH₃), 46.6 (CH₃—CH₂), 58.4(NCH₂), 68.8 (NCH₂), 98.6, 103.3, 132.8 (tert aryl-C), 108.6, 152.6,165.4 (quart. aryl-C), 164.6 (C═N).

EXAMPLE 8

Preparation of

The preparation is carried out in analogy to Example 6, but replacing1,2-diaminocyclohexane with an equivalent amount of1,2-diamino-2-methylpropane.

EXAMPLE 9

Preparation of

A solution of 4.56 g (0.0517 mol) of 1,2-diamino-2-methylpropane in 50ml of ethanol is placed in a vessel. With stirring, a solution of 10.0 g(0.0517 mol) of 4-diethylamino-2-hydroxybenzaldehyde in 50 ml of ethanolis added dropwise at room temperature over 2 h. After stirring for 2 h(DC control acetonitrile/water 9:1), the reaction is complete. Thereaction solution is carefully concentrated and dried under a highvacuum. The crude product obtained is 13.6 g of2-[(2-amino-2-methylpropylimino)-methyl-5-diethylaminophenol in the formof a dark red oil which is then further used without any additionalpurification.

A solution of 13.6 g (0.0517 mol) of2-[(2-amino-2-methylpropylimino)-methyl-5-diethylaminophenol in 50 ml ofethanol is heated to 50° C. and then 5.5 ml (6.31 g, 0.0517 mol) ofsalicylaldehyde are added dropwise over three minutes. The temperatureof the solution rises by 5° C. After refluxing the reaction solution forthree hours, it is allowed to cool and is then concentrated byevaporation. This yields 19.31 g of crude mixture which contains the twodiastereomers (1c′) and (1c). The crude mixture is separated by columnchromatography (ethyl acetate/methanol 9:1). Yield: 4.01 g (21%) (1c′)of a pale beige solid, 1.55 g (8%) (1c) of a pale brown oil. NMR data(1c′):

¹³C NMR (CD₃OD): δ=12.2 (CH₃CH₂N), 23.9 (CH₃)₂C), 44.5 (NCH₂CH₃), 60.1(quart. C(CH₃)₂), 62.0 (═NCH₂), 99.4, 104.3, 117.0, 118.6, 132.4, 132.8,135.6 (tert aryl-C), 108.3, 119.1, 155.2, 162.2 (quart aryl-C), 162.8,163.5 (C═N). NMR data (1c):

¹³C NMR (CD₃OD): δ=12.2 (CH₃CH₂N), 24.7 (CH₃)₂C—), 44.5 (NCH₂CH₃), 57.1(quart. C(CH₃)₂), 69.3 (═NCH₂), 99.6, 104.1, 116.8, 118.9, 132.2, 132.8,135.9 (tert aryl-C), 108.1, 119.1, 155.4, 161.4, 177.0 (quart aryl-C),158.0, 168.4 (C═N).

EXAMPLE 10

Preparation of

0.5 g (2.29 mmol) of 2-(2-aminocyclohexylimino)methylphenol, preparedaccording to Tetrahedron Letters 39 (1998) 4199-4202, is dissolved in 50ml of ethanol until a clear yellow solution is obtained. 378 mg (2.29mmol) of 4-dimethylaminosalicylaldehyde, dissolved in 50 ml of ethanol,are added dropwise at room temperature. After heating the reactionsolution for 4 h to 60° C., it is allowed to cool to room temperatureand is then carefully concentrated in a rotary evaporator, yielding 829mg of a yellow solid. This crude product is purified by separation viacolumn chromatography (silica gel, ethyl acetate/methanol 9:1. Yield:318 mg (38%) of a pale yellow solid.

¹³C NMR (CDCl₃): δ=24.2, 24.4, 33.2, (cycl.—CH₂), 40.0 (N—CH₃), 71.1,72.9 (tert cycl. CH). 98.7, 103.4, 116.7, 118.5, 131.5, 132.0, 132.6(tert aryl-C), 108.7, 118.7, 153.6, 161.1 (quart. aryl-C), 163.2, 164.7(C═N).

EXAMPLE 11

Preparation of

A suspension of 2.5 g (8.64 mmol) of2-[(2-amino-cyclohexylimino)methyl]-5-diethylaminophenol in 200 ml ofethanol is charged dropwise with a solution of 1.3 g (8.64 mmol) of4-methoxysalicylaldehyde in 200 ml of ethanol over 45 minutes at roomtemperature. This reaction solution is heated for 4 h to 60° C. Aftercooling the reaction solution to room temperature, it is concentrated todryness. The crude product obtained is purified by column chromatography(ethyl acetate/methanol 9:1). Yield: 500 mg (14%) of a reddish orangeoil which slowly crystallises.

¹³ C NMR (CDCl₃): δ=12.7 (CH₃CH₂N), 24.3, 33.2 (cycl.—CH₂), 44.4 (CH₃CH₂N), 55.3 (OCH₃), 70.9, 71.5, 71.6 (tert cycl. CH), 98.0, 101.1,103.0, 106.1, 106.2, 132.9 (tert aryl-C), 108.2, 112.3, 151.3, 165.5(quart. aryl-C), 162.9, 163.7 (C═N).

EXAMPLE 12

Preparation of

A solution of 3.87 g (0.0644 mol) of ethylenediamine in 300 ml ofethanol is placed in a vessel and then a solution of 12.45 9 (0.0644mol) of 4-diethylaminosalicylaldehyde in 60 ml of ethanol is slowlyadded dropwise, with stirring, at room temperature. The solution isrefluxed for 2 h. After cooling to room temperature, a solutionconsisting of 9.8 g (0.0644 mol) of 4-methoxysalicylaldehyde in 25 mlethanol is slowly added dropwise and the reaction solution is thenheated for 1 h to reflux temperature. The reaction solution is allowedto cool slowly and is stirred for 8 h at room temperature. For workingup, the resulting yellow suspension is concentrated under vacuum andpurified by column chromatography over silica gel (eluant ethylacetate/methanol 9:1). The asymmetric ligand is isolated in the form ofan orange oil. Yield: 4.00 g (17%). ¹³C NMR (CDCl₃): δ=12.7 (CH₃CH₂N),44.4 (NCH₂CH₃), 55.3 (OCH₃), 58.1, 58.7 (NCH₂), 98.0, 101.2, 103.1,106.3, 132.9, 133.0 (tert aryl-C), 108.3, 112.3, 151.5, 163.5 (quart.aryl-C), 164.5,165.4 (C═N).

EXAMPLE 13

Preparation of(R,R)-N,N′-bis(5-(triethylammoniomethylsalicylidene)-1,2-cyclohexanediaminedihydrochloride

1.09 g (4 mmol) of (5-triethylammoniomethyl)salicylaldehyde chloride(synthesis see T. Tanaka et al., Bull. Chem. Soc. Jpn. 1997, 70,615-629) is dissolved in 10 ml of water and charged with 0.228 g (2mmol) of 1,2-diaminocyclohexane, dissolved in 2 ml of water. The yellowsolution is stirred for 2 h at room temperature and is then concentratedin a rotary evaporator at a bath temperature of 60° C. (10 mbar). 2×50ml of tetrahydrofuran are added and the mixture is again concentrated,yielding 1.22 g of the desired product in the form of yellow crystalsin >90% purity (NMR).

¹³C NMR (D₂O): δ=7.4 (CH₃), 23.8, 31.3, 52.3, 59.6 (aliph. CH₂), 67.7(tert C), 115.0, 116.5 (quart. aryl-C), 121.5, 138.5, 139.4 (tertaryl-C), 166.9 (C═N), 171.5 (quart. aryl-C).

EXAMPLE 14

Preparation ofN,N′-bis(5-(triethylammoniomethyisalicylidene)-1,2-ethandiaminedihydrochloride

The compound is prepared in analogy to the instructions of the precedingExample. This yields yellow crystals in >90% purity (NMR).

¹³C NMR (D₂O) δ=7.4 (CH₃), 52.2, 53.5, 59.6 (aliph. CH₂ in each case),114.6, 116.4 (quart. aryl-C), 120.5, 138.9, 139.6 (tert aryl-C), 168.7(C═N), 172.3 (quart. aryl-C).

EXAMPLE 15

Preparation of(R,R)-N-[4-(dimethylamino)salicylaldehyde]-N′-(2-hydroxyacetophenone)-1,2-cyclohexanediimine

A solution of 2.5 g (9.56 mmol) ofR,R-mono[4-N-(dimethylamino)salicylidene-1,2-cyclohexanediamine in 225ml of ethanol is charged dropwise with 1.30 g (9.56 mmol) of2-hydroxyacetophenone, dissolved in 225 ml of ethanol. This mixture isheated for 8 hours to 60° C. The resulting reddish brown clear solutionis stirred for another 4 hours at room temperature and concentratedunder high vacuum, yielding a crude product (3.6 g, dark red oil) whichis purified by column chromatography (eluant ethyl acetate/methanol9:1). Yield: 1.60 g (44%) of a reddish orange solid, m.p. 129° C.

¹³C NMR (CDCl₃): δ=14.7 (CH₃), 24.2, 24.3, 32.4, 33.2 (cycl. CH₂), 40.0(NCH₃), 62.3, 72.2 (tert cycl. CH), 98.6, 103.4, 116.8, 118.6, 128.3,132.3, 132.7 (tert aryl-C), 108.6, 119.1, 153.6, 164.3, 170.9 (quart.aryl-C), 163.2 (C═N). C₂₃H₂₉N₃O₂ (379.5)

EXAMPLE 16

Preparation of(R,R)-N-[4-(dimethylamino)salicylidene]-N′-(4-hydroxysalicylidene)-1,2-cyclohexanediamine

A solution of 2.5 g (9.56 mmol) of(R,R)-N-mono(4dimethylsalicylidene)-1,2-cyclohexanediamine in 225 ml ofethanol is charged dropwise with a solution of 1.321 g (9.56 mmol) of2,4dihydroxybenzaldehyde in 225 ml of ethanol over 45 minutes at roomtemperature. The reaction solution is heated to 60° C. for 4 h. Aftercooling to room temperature, the resulting reddish brown clear solutionis concentrated to dryness. The crude product (about 5 g) is separatedby column chromatography (ethyl acetate/methanol 9:1). Yield: 1.09 g(30% of a yellowish orange solid), m.p. 202° C.

¹³C NMR (DMSO-d₆): δ=23.7, 32.7, 32.8 (cycl.—CH₂), 40.0 (NCH₃), 70.3,70.7 (tert cycl. CH), 97.9, 102.3, 103.2, 106.7, 132.5, 133.1 (tertaryl-C), 108.1, 111.1, 153.1, 161.4 (quart. aryl-C), 163.4, 163.9 (C═N).C₂₂H₂₇N₃O₃ (381.5)

EXAMPLE 17

Preparation ofN-2-[4diethylamino)salicylidene]-N′-1-(2-hydroxyacetophenone)-2-methylpropane-1,2-diamine

A solution of 500 mg (2.42 mmol) ofN-1-mono(2-hydroxyacetophenone-2-methylpropane-1,2-diamine [preparedaccording to the literature instruction of H. Elias et al, Z.Naturforsch. 49b, 1089 (1994)] in 6 ml of methanol is charged with 478mg (2.42 mmol) of 4-N-diethyl-aminosalicylaldehyde. The orange solutionso obtained is heated for two hours to 80° C. After allowing thereaction solution to cool to room temperature it is concentrated and theresidue is purified by column chromatography (eluant toluene/methanol10:1). Yield: 442 mg (48%) of a yellowish oil.

¹³C NMR (CDCl₃): δ=13.1 (CH₃CH₂N), 15.1 (CH₃), 26.0 (CH₃)₂C), 44.9 (CH₃CH₂N), 59.1 (quart. C(CH₃)₂), 61.3 (CH₂), 98.8, 103.5, 117.5, 119.0128.6 (tert aryl-C), 108.8, 119.7, 152.2, 164.2, 167.5 (quart. aryl-C),159.6 (C═N), 173.0 ((CH₃)C═N).

EXAMPLE 18

Preparation ofN-2-[4-dimethylamino)salicylidene]-N′-1-(2-hydroxyacetophenone)-2-methylpropane-1,2-diamine

A solution of 500 mg (2.42 mmol) ofN-1-mono(2-hydroxyacetophenone-2-methylpropane-1,2-diamine, preparedaccording to the literature reference given in the preceding Example, in6 ml of methanol is charged with 400.3 mg (2.42 mmol) of4-N-dimethylaminosalicylaldehyde. After stirring for 15 minutes at roomtemperature, the resulting yellow solution is heated for 1 hour toreflux temperature. After cooling, the reaction solution is concentratedunder vacuum and the crude product obtained is purified by columnchromatography (eluant ethyl acetate/methanol 11:1). Yield: 642 mg (75%of a yellow solid), melting point 115° C.

¹³C NMR (CDCl₃): δ=13.5 (CH₃), 24.3 ((CH₃)₂C), 38.9 (NCH₃), 57.8 (quart.C(CH₃)₂), 59.7 (CH₂), 97.9, 102.3, 106.7, 115.9, 117.4, 127.0, 131.3,131.9 (tert aryl-C), 107.8, 118.2, 152.8, 162.6, 165.1 (quart. aryl-C),158.5 (C═N), 171.5 ((CH₃)C═N).

EXAMPLE 19

The following application data supplement Example 1. The washingconditions are the same as those given in Example 1:8.6 mmol/L of H₂O₂and 100 μmol/L of catalyst.

Cotton Increase of brightness DY at 40° C. staining in the system withcatalyst with (1k) (1l) (1n) (1m) (1o) (1p) tea 24 22 22 23 24 23

What is claimed is:
 1. A washing and cleaning process, which comprisesadding to a liquor comprising a peroxide-containing washing and cleaningagent, 1-500 μmol per litre of the liquor of a compound of the formula

wherein n is 0, 1, 2or 3, m is 1, 2or 3, R₄ is hydrogen or linear orbranched C₁-C₄alkyl, R₈ is hydrogen or linear or branched C₁-C₄alkyl, Yis a linear or branched alkylene radical of formula —[C(R₄)₂]_(r)—,wherein r is an integer from 1 to 8, and the R₄ groups have eachindependently of one another the meaning given above; —CX═CX—, wherein Xis cyano, linear or branched C₁-C₈alkyl or di(linear or branchedC₁-C₈alkyl)amino, —(CH₂)_(q)—NR₄—(CH₂)_(q)—, wherein R₄ has the meaningrecited above, and q is 1, 2, 3 or 4; or a 1,2-cyclohexylene radical ofthe formula:

or a 1,2-aryl radical of formula

wherein R₉ is hydrogen, SO₃H, CH₂OH or CH₂NH₂, R and R₁ are eachindependently of the other cyano, halogen, OR₄ or COOR₄, wherein R₄ hasthe meaning recited above, nitro, linear or branched C₁-C₈alkyl, linearor branched partially fluorinated or perfluorinated C₁-C₈alkyl, NR₅R₆,wherein R₅ and R₆ are identical or different and are each hydrogen orlinear or branched C₁-C₁₂alkyl, or linear or branched C₁-C₈alkyl-R₇,wherein R₇ is NH₂, OR₄, COOR₄ or NR₅R₆, which have the meanings givenabove, or —CH₂—N⊕R₄R₆R₇ or —N⊕R₄R₅R₆, wherein R₄, R₅ and R₆ have themeanings recited above, R₂ and R₃ are each independently of the otherhydrogen, linear or branched C₁-C₄alkyl or unsubstituted aryl, or arylwhich is substituted by cyano, halogen, OR₄ or COOR₄, wherein R₄ ishydrogen or linear or branched C₁-C₄alkyl, by nitro, linear or branchedC₁-C₈alkyl, NHR₅or NR₅R₆, wherein R₅ and R₆ are identical or differentand are each hydrogen or linear or branched C₁-C₁₂alkyl, or by linear orbranched C₁-C₈alkyl-R₇, wherein R₇is NH₂, OR₄, COOR₄ or NR₅R₆, whichhave the meanings given above, or by —N⊕R₄R₅R₆, wherein R₄, R₅ and R₆have the meanings given above wherein said liquor is then contacted witha surface to be cleaned.
 2. A process according to claim 1, whichcomprises adding to the washing and cleaning liquor 5 to 350 μmol perlitre of washing liquor of a compound of formula (1) or (2).
 3. Aprocess according to claim 1, which comprises adding to the washing andcleaning liquor 10 to 250 μmol per litre of washing liquor of a compoundof formula (1) or (2).
 4. A process according to claim 1, whichcomprises adding a compound of formula (1) or (2), wherein Y is aradical of the formula —(CH₂)_(r)—, wherein r is an integer from 1 to 8,or of the formula —C(R₄)₂—(CH₂)_(p)—C(R₄)₂—, wherein p is a number from0 to 6, and the R₄ groups are each independently of one another hydrogenor C₁-C₄alkyl, or a 1,2-cyclohexylene radical or a 1,2-phenylene radicalof formula:


5. A process according to claim 1, which comprises adding a compound offormula (1) or (2), wherein R and R₁ are hydrogen, OR₄, COOR₄, N(R₄)₂ orN⊕(R₄)₃, wherein the R₄ groups in N(R₄)₂ or N⊕(R₄)₃ may be different andare hydrogen or C₁-C₄alkyl.
 6. A process according to claim 5, whereinthe R₄ groups in N(R₄)₂ or N⊕(R₄)₃ may be different and are hydrogen,methyl, ethyl or isopropyl.
 7. A process according to claim 1, whichcomprises adding a compound of formula (1) or (2), wherein R₂ and R₃ arehydrogen, methyl, ethyl or unsubstituted phenyl.
 8. A process accordingto claim 1, which comprises adding a compound of formula (2), whereineach R₈ is hydrogen.
 9. A process according to claim 1, which comprisesadding a compound of formula


10. A washing and cleaning agent, which comprises I) 5-90% A) of ananionic surfactant and/or B) of a nonionic surfactant, II) 5-70% C) of abuilder substance, III) 0.1-30% D) of a peroxide, and IV) a compound offormula (1) or (2) as defined in claim 1 in an amount which in a washingor cleaning process results in a 1-500 μmolar solution.
 11. A washingand cleaning agent, which comprises I) 5-70% A) of an anionic surfactantand/or B) of a nonionic surfactant, II) 5-50% C) of a builder substance,III) 0.1-12% D) of a peroxide, and IV) a compound of formula (1) or (2)as defined in claim 1 in an amount which in a washing or cleaningprocess results in a 5-350 μmolar solution.
 12. A washing agentaccording to claim 10, which additionally comprises 0.05 to 5% by weightof tetraacetylethylenediamine.